Mechanistic elucidation of the role of metal oxidation states in nickel mediated electrocatalytic coupling of benzyl halides  

作　　者：Pradip K.Das Priyanka Chakraborty Sandeep Suryabhan Gholap Theo P.Gonçalves Changguang Yao Huaifeng Li Zhiping Lai Abdul-Hamid Emwas Kuo-Wei Huang 

机构地区：[1]Division of Physical Sciences and Engineering,King Abdullah University of Science and Technology,Thuwal 23955-6900,Saudi Arabia [2]KAUST Catalysis Center,King Abdullah University of Science and Technology,Thuwal 23955-6900,Saudi Arabia [3]Advanced Membrane and Porous Materials Center,King Abdullah University of Science and Technology,Thuwal 23955-6900,Saudi Arabia [4]KAUST Core labs,King Abdullah University of Science and Technology,Thuwal 23955-6900,Saudi Arabia

出　　处：《Green Synthesis and Catalysis》2020年第2期143-149,共7页绿色合成与催化（英文）

摘　　要：We present the mechanistic understanding of an electrochemically-driven nickel-catalyzed coupling reaction.Computational analysis reveals that the spin density is mostly residing on the nickel(Ni)center when Ni^(II) is reduced to NiI.Ni-mediated halogen atom abstraction through outer-sphere electron-transfer pathway to yield coupling products under mild conditions is demonstrated.Importantly,we have elucidated the role of Ni^(I) and Ni^(0) for successive coupling of benzyl bromide and benzyl chloride derivatives,respectively,to corresponding bibenzyl products.The Ni-catalyst bearing a PN^(3) P-ligand is an effective catalyst,producing a strong ligand effect on the reactivity and selectivity for the homocoupling reactions.

关 键 词：PN^(3) P pincer NICKEL Mechanism Electrocatalysis HOMOCOUPLING 

分 类 号：O62[理学—有机化学]